Thioether containing quartenary ammonium derivatives of 1,4-thiazines

ABSTRACT

This invention relates to N-alkyl thioethers of quaternary ammonium derivatives of 1,4-thiazines; to the preparation thereof; and to the uses thereof for example as corrosion inhibitors, microbiocides, etc.

This is a division of application Ser. No. 886,182, filed Mar. 13, 1978,now U.S. Pat. No. 4,146,709.

This invention relates to novel quaternary ammonium derivatives of1,4-thiazines of the general formula ##STR1## where R is hydrogen, ahydrocarbon group such as alkyl, etc., or a substituted hydrocarbongroup. R' is a hydrocarbon group such as alkyl, cycloalkyl, aralkyl,etc. or a substituted hydrocarbon group. R" is a hydrocarbon group suchas alkyl, cycloalkyl, aralkyl, alkenyl, alkynyl, etc., or a substitutedhydrocarbon group. Z is S, S→O, O←S→O, and X is an anion such as halide,sulfate, phosphate, nitrate, perchlorate or methyl sulfonate, ethylsulfonate, vinyl sulfonate, etc. The preferred derivatives are thosewhere R is hydrogen and it is further preferred that R' be an alkylgroup having about 4 to 18 carbon atoms, a cyclohexyl group or aphenalkyl group and that R" be an alkyl group having 1 to 8 carbonatoms, a cycloalkyl group, an alkynyl group, or an alkenyl group.

These compounds are prepared by reacting a divinyl sulfur compound witha thioether substituted secondary amine. The reaction of secondaryamines with divinyl sulfur compounds is described in my U.S. Pat. No.3,770,732 dated Nov. 6, 1973.

The reaction may be summarized by the following equation: ##STR2## whereR is alkyl, cycloalkyl, aralkyl, etc. and R' is alkyl, alkenyl, alkynl,aralkyl, cycloalkyl, etc. Z is S, S→O, O←S→O.

Examples of the divinyl sulfur compounds are: ##STR3##

Examples of thioether substituted secondary amines capable of reactingwith a divinyl sulfur compound to form the compounds of this inventioninclude, for example: ##STR4##

These compounds are obtained in good yield by utilizing a modificationof the procedure described by O. Landini and F. Rolla, Synthesis 1974,p. 565.

Suitable acids that may be employed to form the amine salts includehydrohalic acids such as hydrochloric, hydrobromic, hydroiodic, etc.;sulfuric, phosphoric, nitric, perchloric, methylsulfonic, ethylsulfonic,benzyl sulfonic, and the like.

In carrying out the reaction it is preferred to form the amine salt insitu, that is in a solvent such as ethanol in which it is soluble.However, if desired, the salt may first be isolated and purified. To thesolution of the amine salt in a suitable inert solvent is added thedivinyl sulfur compound. The preferred temperature is about 20° to 50°C. though higher or lower temperatures may be employed. A catalyst suchas triethylamine may be used. In most instances the thiazine quaternaryammonium salt precipitates from the alcoholic medium and is purified byrecrystallization. In some cases it is necessary to reduce the finalvolume in order to isolate the desired product.

The invention may be illustrated by the following examples.

EXAMPLE 1

Divinyl sulfone 5.9 g (0.05 mol) was added dropwise, with stirring, to asolution of ##STR5## 9.6 g. (0.05 mol) in 25 ml. of 4 N ethanolichydrochloric acid. The mixture became warm and upon cooling crystalsappeared. After 24 hrs. the crystalline product was filtered and washedseveral times with cold ethanol. The product was recrystallized fromaqueous ethanol.

Yield: 14.6 g. (85%).

Anal. C₁₄ H₃₀ ClNO₂ S₂ --Calc. C, 48.91; H, 11.46; Cl, 10.32; S, 18.61;N, 4.07. Found: C, 48.89; H, 11.43; Cl, 10.29; S, 18.64; N, 4.11.

The product had the following structure which was confirmed by NMRspectrum. ##STR6##

EXAMPLE 2

Divinyl sulfone 5.9 g. (0.05 mol) was added dropwise with stirring to asolution of ##STR7## 13.6 g. (0.05 mol) in 30 ml. of 4 N ethanolichydrochloric acid. The resulting reaction mixture was heated at refluxfor 2 hours. Upon cooling, a waxy solid separated. The solid wasfiltered and washed with cold ethanol.

Yield: 29 g (79%)

Anal.--Calc. N, 1.84; Found N, 1.75.

The product had the following structure ##STR8##

EXAMPLE 3

Divinyl sulfone 5.9 g. (0.05 mol) was slowly added to a solution of##STR9## 12.1 g. (0.05 mol) in 30 ml. of ethanol that had been acidifiedwith 7.7 g. (0.06 mol) of hydroiodic acid. The reaction mixture becomeswarm. After 24 hours the reaction mass contained a large mass ofcolorless crystals. The crystals were filtered and washed with coldethanol.

Yield: 21 g. (90%).

The product was recrystallized from aqueous ethanol. It had thefollowing structure: ##STR10##

Anal.--Calcd. N, 2.98; S, 13.64; I, 27.08. Found N, 3.04; S, 13.48; I,27.32.

In a similar manner the following examples were prepared.

    ______________________________________                                         ##STR11##                                                                    Example                                                                       ple     R'           R"             X.sup.⊖                           ______________________________________                                        4       C.sub.6 H.sub.5 CH.sub.2 CH.sub.2                                                          C.sub.6 H.sub.5 CH.sub.2                                                                     Cl                                        5       C.sub.4 H.sub.9                                                                            C.sub.6 H.sub.11                                                                             Br                                        6       C.sub.10 H.sub.21                                                                          C.sub.2 H.sub.5                                                                              Br                                        7       C.sub.4 H.sub.9                                                                            C.sub.8 H.sub.17                                                                             I                                         8       C.sub.6 H.sub.11                                                                           C.sub.6 H.sub.11                                                                             I                                         9       C.sub.14 H.sub.29                                                                          CH.sub.3       SO.sub.3                                  10      C.sub.18 H.sub.37                                                                          CH.sub.3       I                                         11      C.sub.4 H.sub.9                                                                            CHCCH.sub.2    Br                                        12      C.sub.4 H.sub.9                                                                             ##STR12##     Cl                                        13      C.sub.12 H.sub.25                                                                          CH.sub.3       I                                         14      C.sub.4 H.sub.9                                                                            CH.sub.2CHCH.sub.2                                                                           Br                                    

USES

This invention also relates to the inhibition of corrosion, particularlythe corrosion of metals in contact with the acid solutions.

The present invention is especially useful in the acidizing or treatingof earth formations and wells traversed by a bore hole. It may also beused in metal cleaning and pickling baths which generally compriseaqueous solutions of inorganic acids such as sulfuric acid, hydrochloricacid, phosphoric acid and are useful in the cleaning and treatment ofiron, zinc, ferrous alloys, and the like.

If no corrosion inhibitor is present when the aqueous acidic solutioncomes in contact with the metal, excessive metal loss and consumption orloss of acid, and other adverse results will be experienced. There hasbeen a continuing search for corrosion inhibitors which can be usedeffectively in small concentrations, and which are economical toproduce. The need is also for corrosion inhibitors which are effectiveat high temperatures, e.g., 200° F. and above, such as are found inoperations involving acidic solutions, particularly oil-well acidizingwhere higher and higher temperatures are found as the well extendsfurther into the earth.

While the compounds of this invention are of themselves particularlygood acid corrosion inhibitors, optionally they may be blended withacetylenic alcohols, dispersing and solubilizing agents such asethoxylated phenols, alcohols, and fatty acids. They may also be blendedwith such known acid inhibitors as the quinoline or alkyl pyridinequaternary compounds or synergists such as terpene alcohols, formamide,formic acid, alkyl amine, alkylene polyamines, heterocyclic amines, andthe like.

Quaternary ammonium compounds may be illustrated by C-alkylpyridine-N-methyl chloride quaternary, C-alkyl pyridine-N-benzylchloride quaternary, quinoline-N-benzyl chloride quaternary,isoquinoline-N-benzyl chloride quaternary, thioalkyl pyridinequaternaries, thioquinoline quaternaries, benzoquinoline quaternaries,thiobenzoquinoline quaternaries, imidazole quaternaries, pyrimidinequaternaries, carbazole quaternaries, the corresponding ammoniumcompounds, pyridines and quinolines may also be used alone or incombination with the quaternary compounds. Thus a pyridine plusquinoline quaternary, a quinoline plus quinoline quaternary, orquinoline or amine alone or in combination may be used.

The formic acid compound may be selected from the esters and amides offormic acid. The formic acid compound may be from the group consistingof formate esters of the structure:

    HCOOR

where R is a monoaryl group, an alkyl group having 1 to 6 carbon atoms,cyclo-alkyl residues having 5 to 6 carbon atoms, alkenyl and alkynlgroups having 2 to 6 carbon atoms which may contain functional groupingsselected from --C--OH, --OH, ═C═O, --COOH, --SH, and NH₂. Examples ofthe formic acid compound are: methyl formate, ethylformate, benzylformate, other alkyl and aryl formates, and the like. Other examplesinclude formamide, dimethyl formamide, formanilide, and the like.Mixtures of the esters and mixtures of the amides may be used.

USE IN ACIDIZING EARTH FORMATIONS

The compositions of this invention can also be used as corrosioninhibitors in acidizing media employed in the treatment of deep wells toreverse the production of petroleum or gas therefrom and moreparticularly to an improved method of acidizing a calcareous ormagnesium oil-bearing formation.

It is well known that production of petroleum or gas from a limestone,dolomite, or other calcareous-magnesian formation can be stimulated byintroducing an acid into the producing well and forcing it into the oilor gas bearing formation. The treating acid, commonly a mineral acidsuch as HCl, is capable of forming water soluble salts upon contact withthe formation and is effective to increase the permeability thereof andaugment the flow of petroleum to the producing well.

Corrosion Test Procedure

In these tests the acid solutions were mixed by diluting concentratedhydrochloric acid with water to the desired concentrations.

Corrosion coupons of AISI 1020 Steel were pickled in an uninhibited 10%HCl solution for 10 minutes, neutralized in a 10% solution of NaHCO₃,dipped in acetone to remove water and allowed to dry. They were thenweighed to the nearest milligram and stored in a desicator.

In most of the tests, a 25 cc/in² acid volume to coupon surface arearatio was used. After the desired amount of acid was poured into glassbottles, the inhibitor was added. The inhibited acid solution was thenplaced in a water bath which had been set at a predetermined temperatureand allowed to preheat for 20 minutes. After which time, the couponswere placed in the preheated inhibited acid solutions. The coupons wereleft in the acid solutions for the specified test time, then removed,neutralized, recleaned, rinsed, dipped in acetone, allowed to dry, thenreweighed.

The loss in weight in grams was multiplied times a calculated factor toconvert the loss in weight to lbs./ft² /24 hrs. The factor wascalculated as follows: ##EQU1##

The results of these tests are included below:

    ______________________________________                                                        Test     Test         Corrosion                                               Temp     Time         Rate                                    Inhibitor                                                                             p.p.m.  °F.                                                                             Hrs. Acid    (lbs./ft.sup.2 /day)                    ______________________________________                                        Ex. 1   2000    150      4    15% HCl 0.075                                   Ex. 2   2000    150      4    15% HCl 0.029                                   Ex. 3   2000    150      4    15% HCl 0.050                                   Ex. 6   2000    150      4    15% HCl 0.041                                   Ex. 9   2000    150      4    15% HCl 0.031                                   Ex. 10  2000    150      4    15% HCl 0.030                                   Ex. 11  2000    150      4    15% HCl 0.035                                   Ex. 13  2000    150      4    15% HCl 0.025                                   Ex. 14  2000    150      4    15% HCl 0.068                                   Blank           150      4    15% HCl 0.275                                   ______________________________________                                    

Applications in which the inhibitors of the present invention areparticularly useful include oil-well acidizing solutions, metalpickling, cleaning and polishing baths, boiler cleaning compositions andthe like. They are also useful as oil soluble corrosion inhibitors,bactericides, water-in-oil demulsifying agents, surfactants and thelike.

USE AS A MICROBIOCIDE (I) In Water Treatment

This phase of the present invention relates to the treatment of water.More particularly, it is directed to providing improved means forcontrolling microbiological organisms including bacteria, fungi, algae,protozoa, and the like, present in water.

It is well known that ordinary water contains various bacteria, fungi,algae, protozoa and other microbiological organisms which, ifuncontrolled, multiply under certain conditions so as to present manyserious problems. For example, in swimming pools the growth of thesemicrobiological organisms is very undesirable from a sanitary standpointas well as for general appearances and maintenance. In industrial watersystems such as cooling towers, condenser boxes, spray condensers, watertanks, basins, gravel water filters, and the like, microbiologicalorganisms may interfere greatly with proper functioning of equipment andresult in poor heat transfer, clogging of systems and rotting of woodenequipment, as well as many other costly and deleterious effects.

In other industrial applications where water is used in processes, asfor example, as a carrying medium, etc., microbiological organisms mayalso constitute a problem in maintenance and operation. Illustrative ofsuch industrial applications are the pulp and paper manufacturingprocesses, oil well flooding operations and the like.

The products of this invention are suitable as biocides for industrial,agricultural and horticultural, military, hygienic and recreationalwater supplies. They provide an inexpensive, easily prepared group ofproducts which can be used, in minimal amounts, in water supplies, incooling towers, air-conditioning systems, on the farm and ranch, in thefactory, in civilian and military hospitals and dispensaries, in camps,for swimming pools, baths and aquaria, waterworks, wells, reservoirs, byfire-fighting agencies, on maritime and naval vessels, in boilers, steamgenerators and locomotives, in pulp and paper mills, for irrigation anddrainage, for sewage and waste disposal, in the textile industry, in thechemical industries, in the tanning industry, et cetera, and which willrender said water supplies bactericidal, fungicidal and algicidal. Theyfurther provide a simple process whereby water supplies, for whateverpurposes intended, are rendered bacteriostatic, fungistatic andalgistatic, i.e., said water supplies treated by the process of thisinvention will resist and inhibit the further growth or proliferation ofbacteria, fungi, algae and all forms of microbial life therein.

(II) Water Flooding in Secondary Recovery of Oil

This phase of the present invention relates to secondary recovery of oilby water flooding operations and is more particularly concerned with animproved process for treating flood water and oil recovery therewith.More particularly this invention relates to a process of inhibitingbacterial growth in the recovery of oil from oil-bearing strata by meansof water flooding taking place in the presence of sulfate-reducingbacteria.

Water flooding is widely used in the petroleum industry to effectsecondary recovery of oil. By employing this process the yield of oilfrom a given field may be increased beyond the 20-30 percent of the oilin a producing formation that is usually recovered in the primaryprocess. In flooding operation, water is forced under pressure throughinjection wells into or under oil-bearing formations to displace the oiltherefrom to adjacent producing wells. The oil-water mixture is usuallypumped from the producing wells into a receiving tank where the water,separated from the oil, is siphoned off, and the oil then transferred tostorage tanks. It is desirable in carrying out this process to maintaina high rate of water injection with a minimum expenditure of energy. Anyimpediment to the free entry of water into oil-bearing formationsseriously reduces the efficiency of the recovery operation.

The term "flood water" as herein employed is any water injected intooil-bearing formations for the secondary recovery of oil. Inconventional operations, the water employed varies from relatively purespring water to brine and is inclusive of water reclaimed from secondaryrecovery operations and processed for recycling. The problems arisingfrom the water employed depend in part on the water used. However,particularly troublesome and common to all types of water are problemsdirectly or indirectly concerned with the presence of microorganisms,such as bacteria, fungi and algae. Microorganisms may impede the freeentry of water into oil-bearing formations by producing ions susceptibleof forming precipitates, forming slime and/or existing in sufficientlyhigh numbers to constitute an appreciable mass, thereby plugging thepores of the oil-bearing formation. Free-plugging increases the pressurenecessary to drive a given volume of water into an oil-bearing formationand oftentimes causes the flooding water to by-pass the formation to beflooded. In addition, microorganisms may bring about corrosion by actingon the metal structures of the wells involved, producing corrosivesubstances such as hydrogen sulfide, or producing conditions favorableto destructive corrosion such as decreasing the pH or producing oxygen.The products formed as the result of corrosive action may also bepore-plugging precipitates. Usually, the difficulties encountered are acombination of effects resulting from the activity of differentmicroorganisms.

(III) Hydrocarbon Treatment

This phase of the present invention relates to the use of thesecompounds as biocides in hydrocarbon systems.

In addition to being used as biocides in aqueous systems, the compoundsof this invention can also be employed as biocides in hydrocarbonsystems, particularly when petroleum products are stored. It is believedthat bacteria and other organisms, which are introduced into hydrocarbonsystems by water, feed readily on hydrocarbons resulting in a loss inproduct; that microorganisms cause the formation of gums, H₂ S,peroxides, acids and slimes at the interface between water and oil; thatbacterial action is often more pronounced with rolling motion than understatic conditions, etc. Loss of product, corrosion of the storage tank,clogging of filters and metering instruments, and fuel deterioration areamong the harmful effects of bacteria growth in fuels. The activity ofmicroorganism growth is often increased by the presence of rust. Notonly do these microorganisms often encourage rust but rust encouragesmicroorganism growth. Since microorganism growth appears to beconsiderably higher with kerosene than with gasoline, plugged filtersexperienced with jet fuels which contain large amounts of kerosene is aserious problem.

The compositions of this invention can be employed in hydrocarbonsystems.

Microbiocidal Testing

The screening procedure was as follows: a one percent by weight solutionof the test compound in water was prepared. The solution was asepticallyadded to a sterile broth that would support the growth of the testorganism, Desulfovibro desulfuricans, to provide a concentration of 25,50, 75 and 100 parts by weight of test compound per million parts byweight of broth. A general growth medium, such as prescribed by theAmerican Petroleum Institute was used. The broth containing the testcompound then was dispersed in 5 cc. amounts into sterile disposabletubes and the tubes were inoculated with the growing test organism andincubated at 35° C. for 24 hours. The absence or presence of growth ofthe microorganisms was determined by visual inspection by an experiencedobserver.

Following is a summary of the results of the testing of examples of thisinvention.

    ______________________________________                                        Compound Example                                                                             Concentration of Test Compound                                 ______________________________________                                        2              50                                                             3              100                                                            5              75                                                             9              25                                                             10             50                                                             13             25                                                             ______________________________________                                    

In all of the above tests no growth of the test organism occurred, thusindicating that the compound is a biostatic or a biocide.

I claim:
 1. A process inhibiting corrosion which comprises treating asystem with a composition characterized by the formula ##STR13## where Ris hydrogen, or a hydrocarbon group, R' is a hydrocarbon group, R" is ahydrocarbon group, Z is S, SO, or SO₂ and X is an anion.
 2. The processof claim 1 wherein R' is an alkyl group having about 4 to 18 carbons, acyclohexyl group or a phenalkyl group, and R" is an alkyl group havingabout 1-8 carbons, a cycloalkyl group, an alkynyl group, or an alkenylgroup.
 3. The process of claim 2 where the composition has the formula##STR14## where R' is an alkyl group having 8-18 carbons.
 4. The processof claim 3 where the composition has the formula ##STR15##
 5. Theprocess of claim 3 where the composition has the formula ##STR16##